EP1326292A1 - THERMOELEKTRISCHES UMSETZUNGSMATERIAL UND THERMOELEKTRISCHES UMSETZUNGSELEMENT DER Bi-GRUPPE - Google Patents

THERMOELEKTRISCHES UMSETZUNGSMATERIAL UND THERMOELEKTRISCHES UMSETZUNGSELEMENT DER Bi-GRUPPE Download PDF

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Publication number
EP1326292A1
EP1326292A1 EP01958472A EP01958472A EP1326292A1 EP 1326292 A1 EP1326292 A1 EP 1326292A1 EP 01958472 A EP01958472 A EP 01958472A EP 01958472 A EP01958472 A EP 01958472A EP 1326292 A1 EP1326292 A1 EP 1326292A1
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EP
European Patent Office
Prior art keywords
thermoelectric conversion
magnetic field
elements
temperature side
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01958472A
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English (en)
French (fr)
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EP1326292A4 (de
Inventor
Osamu Yamashita
Yasuhisa Katayama
Yasuyuki Nakamura
Tsunekazu Saigo
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Hitachi Metals Ltd
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Sumitomo Special Metals Co Ltd
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Priority claimed from JP2000253539A external-priority patent/JP2002064228A/ja
Application filed by Sumitomo Special Metals Co Ltd filed Critical Sumitomo Special Metals Co Ltd
Publication of EP1326292A1 publication Critical patent/EP1326292A1/de
Publication of EP1326292A4 publication Critical patent/EP1326292A4/de
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect

Definitions

  • thermoelectric conversion materials for forming the above-described elements.
  • thermoelectric conversion elements temperature gradient is provided between p-type and n-type thermoelectric conversion materials to convert heat into electricity.
  • thermoelectric conversion elements that convert electricity into heat if a voltage is applied to the materials, that is, as Peltier elements.
  • thermoelectric conversion elements The conversion efficiency of thermoelectric conversion elements is very low, for example, by comparison with that (about 20%) of solar cells and does not exceed several percent, and is the main reason for the delayed practical use of thermoelectric conversion elements.
  • thermoelectric material having temperature gradient generation of electric field under magnetic field applied to a thermoelectric material having temperature gradient.
  • Nernst effect L. D. Landau, E. M. Lifslitz, and L. P. Pitaevskli “Electrodynamics of Continuous Media", 2nd Edition, Pergamon Press, P. 101 (1984)).
  • thermoelectric conversion material with an optimum composition for employing a synergistic effect of the Seebeck effect and Nernst effect to increase a thermoelectromotive force of the material.
  • thermoelectric conversion element in which the Seebeck coefficient is increased by applying a magnetic field to a thermoelectric conversion material with a strong Nernst effect, in view of the fact that improvement of material characteristics of the thermoelectric conversion material alone can result only in limited increase in thermoelectric conversion efficiency.
  • thermoelectric conversion materials capable of employing a synergistic effect of the Seebeck effect and Nernst effect and have discovered that the Seebeck effect can be increased substantially by applying a magnetic field to a Bi-based thermoelectric conversion material in which Bi contains no more than 5 at. % required additional elements added solely or in combination thereof.
  • the present invention provides a Bi-based thermoelectric conversion material in which Bi contains at least one of Group VI elements, rare earth elements, alkali metal elements, and alkaline earth metal elements, this thermoelectric conversion material demonstrating n-type conductivity, and a Bi-based thermoelectric conversion material in which Bi contains at least one of transition metal elements, Group III elements, and Group IV elements, this thermoelectric conversion material demonstrating p-type conductivity.
  • thermoelectric conversion efficiency is increased despite a comparatively small temperature gradient by using different electrode materials on a high-temperature side and low-temperature side provided with the difference in temperature.
  • thermoelectric conversion element comprising means for applying magnetic field H in the required direction (x axis direction) of a Bi-based thermoelectric conversion material demonstrating p-type and n-type conductivity, means for providing temperature gradient T in the direction (z axis direction) perpendicular to the aforesaid direction. and means for mounting respective electrode materials on the high-temperature side and low-temperature side of the temperature in the plane with a direction (y axis direction) perpendicular to the two aforesaid directions.
  • thermoelectric conversion element which uses a permanent magnet as means for applying magnetic field H, wherein the conversion efficiency can be greatly increased by using:
  • carrier concentration can be changed by various additional elements and the Nernst effect can be augmented by the prescribed carrier concentration.
  • the capacity index is also increased because electric resistivity is ten or more times less than that of the conventional Bi 2 Te 3 system, Si-Ge system, and Fe-Si system.
  • a material demonstrating n-type conductivity can be obtained by adding Group VI elements, rare earth elements, alkali metal elements, and alkaline earth metal elements to Bi, and a material demonstrating p-type conductivity can be obtained by adding transition metal elements, Group III elements and Group IV elements to Bi.
  • S, Se, Te are the preferred Group VI elements
  • La, Ce, Pr. Nd, Sm, Eu, Gd, Tb, Dy are the preferred rare earth elements
  • Li, Na, K are the preferred alkali metal elements
  • Be, Ma, Ca, Sr, Ba are the preferred alkaline earth metal elements.
  • Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn are the preferred transition metal elements
  • B, Al, Ge, In are the preferred Group III elements
  • C, Si, Ce, Sn, Pb are the preferred Group IV elements.
  • thermoelectric conversion element in accordance with the present invention will be explained below. Under the assumption that a Bi-based thermoelectric conversion material 1 in the shape of a rectangular parallelepiped shown in FIG. 1A is placed on a heat source, the temperature gradient ⁇ T will be provided in the z axis direction from the bottom upwards. Magnetic field H is applied in the x axis direction from the front of the figure backward.
  • electrodes 2, 3 made of different materials are provided on the side with a high temperature T, which is the lower side on the left surface of Bi-based thermoelectric conversion material 1, as shown in the figure, and the side with a low temperature T, which is the upper side on the right surface, respective leads are connected to the electrodes, and thermoelectromotive force is led out therefrom.
  • magnetic field H is applied in the direction perpendicular to the direction of temperature gradient ⁇ T and electrodes are arranged so that a difference in temperature is provided in the plane in the direction perpendicular to the directions of temperature gradient ⁇ T and magnetic field H, that is, the difference in temperature is provided between the positive and negative electrodes.
  • the Seebeck coefficient of Bi-based thermoelectric conversion element 1 is greatly increased even if the applied magnetic field H is low.
  • the difference in temperature between electrodes 2, 3 is decreased, the generated electromotive force is due only to the Nernst effect produced by magnetic field H, and a large electromotive force cannot be obtained. Therefore, if the difference in temperature between electrodes 2, 3 is made no less than 1°C, the Seebeck coefficient is greatly increased by a synergistic effect of thermoelectric effect and Nernst effect. If this difference in temperature exceeds 5°C, the results are practically the same, even if a larger difference in temperature is provided. Furthermore, the preferred temperature is 50 ⁇ 100°C, but sufficient magnetic field effect is demonstrated even at a temperature of several hundreds of degrees.
  • thermoelectric conversion efficiency even if the temperature gradient is comparatively small.
  • one of Ag, Pt, Cu, Ti, In, Pb, Sn, Bi, or alloys thereof be used on the high-temperature side and one of Cu, Pt, Al, Au, Fe, Mo, Zn, In, Pb, Sn, Bi, or alloys thereof be used on the low-temperature side, this material being different from that on the low-temperature side.
  • alloys thereof used hereinabove obviously covers the alloys of the metals within the above-listed groups, but also includes alloys of metals from those groups and other metals.
  • the strength of magnetic field H is no specific limitation placed on the strength of magnetic field H, but if it is no less than 1 kOe, the above-mentioned synergistic effect functions effectively.
  • the preferred strength of magnetic field is no less than 3 k0e.
  • Any apparatus generating magnetic field such as an electromagnetic coil, a superconductive magnet, and the like, and not only the permanent magnet, can be used as means for applying the magnetic field.
  • a magnetic field generated with a rare earth permanent magnet of a Sm-Co system or Ng-Fe-B system is extremely suitable in practical applications for thermoelectric conversion elements incorporating permanent magnets.
  • a permanent magnet of a Sm-Co system (Tc-900°C) with a high Curie point is preferably used as the magnet for magnetic field generation
  • a permanent magnet of Nd-Fe-B system is preferably used at a temperature of less than 300°C.
  • thermoelectric conversion materials and permanent magnets When the Bi-based thermoelectric conversion materials and permanent magnets are arranged alternately, the above-described rare earth magnets demonstrate electric conductivity of metals. Therefore, it is preferred that the thermoelectric conversion materials and permanent magnets be electrically insulated from each other, that is, that they be insulated by coating an electrically insulating film on the surface of thermoelectric conversion materials or permanent magnets or both.
  • thermoelectric conversion material can be appropriately used for the electrically insulating film. It is especially preferred that a polyimide film or alumina film with good electric insulation properties be coated. The sufficient coating thickness is no more than several micrometers. Decreasing thickness of the film can make the gap between the magnets equal to the thickness of thermoelectric conversion material, thereby greatly suppressing the decrease in magnetic flux.
  • a polyimide film or alumina film is appropriately selected depending on the usage temperature. If the usage temperature is no higher than 700K, any of the two films can be used, and when the temperature is higher than 700K, the alumina film is appropriate.
  • the thermoelectric conversion material is coated on the portion which is to become an electrode, it is preferably masked in advance so as to prevent adhesion of the electrically insulating film.
  • thermoelectric materials have an electric resistivity of an order of 10 -6 ( ⁇ m)
  • using as means for applying an electric potential difference for cooling or heating has an advantage of obtaining a large electric current even if the applied voltage is decreased, and modularization of Peltier elements with a high cooling-heating efficiency at a low difference in electric potential becomes possible.
  • Thermoelectric conversion elements of various structures can be assembled by using the p-type Bi-based thermoelectric conversion material and n-type Bi-based thermoelectric conversion material with the structure shown in FIG. 1A. Furthermore, in terms of modularizing the thermoelectric conversion elements with a magnetic field applied thereto, as shown in FIG.
  • wires 7, 8 composed of p/n-joined different materials can be connected separately for a high-temperature side and low-temperature side by arranging the directions of magnetic fields H (x axis direction) of permanent magnets 6 in parallel and perpendicular to the direction (z axis direction) of temperature gradient ⁇ T and arranging the p-type Bi-based thermoelectric conversion materials 4 and n-type Bi-based thermoelectric conversion materials 5 alternately so as to sandwich the permanent magnets 6.
  • the structure of the closed magnetic circuit in the thermoelectric conversion element using the Bi-based thermoelectric conversion material will be explained below based on FIG. s 2A, B.
  • the closed magnetic circuit is obtained by arranging in parallel the blocks of the same structure as shown in FIG. 1B in which a plurality of permanent magnets 6, p-type Bi-based thermoelectric conversion materials 4, and n-type Bi-based thermoelectric conversion materials 5 in the shape of a rectangular parallelepipeds and connecting the permanent magnets 6 on both ends of each block with sheets 9 of a magnetic material such as iron or the like.
  • the rectangular parallelepiped shape shown in the figure or a rod-like shape is desired.
  • a design is required such that the Bi-based thermoelectric conversion materials 5 are longer than the permanent magnets 6 in the direction of temperature gradient and directly connected to a cooling-heating plate or heating plate 10, so that heat is not conducted through the permanent magnets 6.
  • thermoelectric conversion element when a thermoelectric conversion element is composed of p-type and n-type pairs and the structure is, for example, such that a p-type thermoelectric conversion material 4 is located on the left end, as shown by directions along three axis in FIG. 1B, wires 8 on the low-temperature side (low-potential side) are connected to the lower side of the back end surface shown in the figure, wires 7 on the high-temperature side (high-potential side) are connected to the upper side of the front end surface, and other ends thereof are connected to the same potential side of n-type thermoelectric conversion materials 5 adjacent thereto via permanent magnets 6.
  • n-type Bi thermoelectric conversion materials are used and wiring is made alternately from the high-temperature side to the low-temperature side.
  • the wiring similar to that shown in FIG. 2B is also made when only p-type thermoelectric conversion materials are used.
  • thermoelectric conversion materials In order to fabricate n-type and p-type Bi-based thermoelectric conversion materials, elements shown in Table 1 were mixed with high-purity Bi (4N) in the predetermined ratios and the mixture was vacuum sealed in a quartz tube and high-frequency melted. The obtained ingot in the form of a circular rod was machined to obtain a 10 ⁇ 10 ⁇ 1 mm shape and a Hall coefficient was measured to verify the polarity and carrier concentration. The results are shown in Table 2.
  • the ingot was then cut to the size and shape shown in FIG. 3, Seebeck coefficient and Seebeck current were measured, and output power was calculated.
  • Seebeck coefficient and Seebeck current of the sample the voltage of In-soldered copper wire on both ends of the thermoelectric material was measured by changing the magnetic field applied to the thermoelectric material at a constant average temperature of the high-temperature side and low-temperature side of 50°C and a constant difference in temperature of 5°C.
  • the strength of magnetic field was adjusted by changing the spacing between the Nd-Fe-B permanent magnets. Furthermore, the power generated at this time was determined by measuring the voltage ( ⁇ V/K) and current value ( ⁇ A/K) per unit temperature. The measurement results are shown in Table 3. No. Composition (at%) Bi Added elements Amount added (at%) Polarity A 100 - 0. n B 100 Ga 0. n C 100 Ga 5. p D 100 In 11. n E 100 S 1. n No.
  • thermoelectric element on the high-temperature side and low-temperature side makes it possible to increase substantially a thermoelectric conversion efficiency by comparison with that obtained when metal electrodes of the same kind were used, even when the temperature gradient is comparatively small.
  • thermoelectric conversion element when a thermoelectric conversion element is constructed, a structure is employed in which magnetic field is generated by permanent magnets. Therefore, the advantage of the present invention is that a thermoelectric conversion element of a comparatively simple structure can be easily fabricated and maintenance-free used.
EP01958472A 2000-08-24 2001-08-24 THERMOELEKTRISCHES UMSETZUNGSMATERIAL UND THERMOELEKTRISCHES UMSETZUNGSELEMENT DER Bi-GRUPPE Withdrawn EP1326292A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2000253539 2000-08-24
JP2000253539A JP2002064228A (ja) 2000-06-09 2000-08-24 Ｂｉ基熱電変換材料と熱電変換素子
PCT/JP2001/007264 WO2002017406A1 (fr) 2000-08-24 2001-08-24 Matiere de conversion thermoelectrique du groupe bi et element de conversion thermoelectrique

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EP1326292A1 true EP1326292A1 (de) 2003-07-09
EP1326292A4 EP1326292A4 (de) 2007-02-14

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WO (1) WO2002017406A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009052920A3 (de) * 2007-10-22 2009-08-20 O Flexx Technologies Gmbh Thermoelektrischer generator
WO2014200231A1 (ko) * 2013-06-10 2014-12-18 한국과학기술원 원자수준-해상도 주사 제벡 현미경 이미지의 컴퓨터 원용 시뮬레이션 방법
WO2019117719A1 (en) 2017-12-12 2019-06-20 Helios Nova B.V. Generator

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Publication number Priority date Publication date Assignee Title
US3090207A (en) * 1962-03-22 1963-05-21 Bell Telephone Labor Inc Thermoelectric behavior of bismuthantimony thermoelements
US3289422A (en) * 1965-08-16 1966-12-06 Joseph V Fisher Cooling apparatus for infrared detecting system
EP1193774A1 (de) * 1999-06-02 2002-04-03 Asahi Kasei Kabushiki Kaisha Thermoelektrisches material und seine herstellungsmethode

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JP2517103B2 (ja) * 1989-03-13 1996-07-24 松下電器産業株式会社 薄膜熱電素子
JPH03165077A (ja) * 1989-11-22 1991-07-17 Idemitsu Petrochem Co Ltd 熱電素子の製造方法
JPH05259514A (ja) * 1992-03-16 1993-10-08 Matsushita Electric Ind Co Ltd 熱電装置、その製造方法及び製造装置
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Publication number Priority date Publication date Assignee Title
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US3289422A (en) * 1965-08-16 1966-12-06 Joseph V Fisher Cooling apparatus for infrared detecting system
EP1193774A1 (de) * 1999-06-02 2002-04-03 Asahi Kasei Kabushiki Kaisha Thermoelektrisches material und seine herstellungsmethode

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Title
HEREMANS J ET AL: "Thermoelectric power of bismuth nanowires" PHYSICAL REVIEW B (CONDENSED MATTER) APS THROUGH AIP USA, vol. 59, no. 19, 15 May 1999 (1999-05-15), pages 12579-12583, XP002410367 ISSN: 0163-1829 *
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009052920A3 (de) * 2007-10-22 2009-08-20 O Flexx Technologies Gmbh Thermoelektrischer generator
WO2014200231A1 (ko) * 2013-06-10 2014-12-18 한국과학기술원 원자수준-해상도 주사 제벡 현미경 이미지의 컴퓨터 원용 시뮬레이션 방법
US9081030B2 (en) 2013-06-10 2015-07-14 Korea Advanced Institute Of Science And Technology Computer-aided simulation method for atomic-resolution scanning seebeck microscope (SSM) images
US9459278B2 (en) 2013-06-10 2016-10-04 Korea Advanced Institute Of Science And Technology Computer-aided simulation method for atomic-resolution scanning seebeck microscope (SSM) images
WO2019117719A1 (en) 2017-12-12 2019-06-20 Helios Nova B.V. Generator
NL2020065B1 (en) * 2017-12-12 2019-06-21 Helios Nova B V Generator
US11871670B2 (en) 2017-12-12 2024-01-09 Helios Nova B.V. Generator

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WO2002017406A1 (fr) 2002-02-28
EP1326292A4 (de) 2007-02-14

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